CN114008132A

CN114008132A - Polypropylene resin composition containing ultrahigh molecular weight propylene polymer (copolymer)

Info

Publication number: CN114008132A
Application number: CN202080043574.0A
Authority: CN
Inventors: 横山裕; 梶冈宽; 神村尧洋; 秋永修志
Original assignee: Showa Denko KK; SunAllomer Ltd
Current assignee: SunAllomer Ltd; Resonac Holdings Corp
Priority date: 2019-06-17
Filing date: 2020-06-12
Publication date: 2022-02-01
Anticipated expiration: 2040-06-12
Also published as: CN114008132B; EP3985035A4; JPWO2020255873A1; US20220177686A1; TW202108685A; WO2020255873A1; EP3985035A1

Abstract

A polypropylene resin composition comprising the following components (A1) and (A2), wherein the content of the component (A1) is 0.1 to 10% by weight and the content of the component (A2) is 99.9 to 90% by weight based on the total amount of the components, wherein the component (A1) is a propylene homopolymer or a copolymer of propylene and 30% by weight or less of an alpha-olefin having 2 or 4 to 8 carbon atoms, the intrinsic viscosity measured in a tetralin solvent at 135 ℃ is more than 20dl/g, the MFR (230 ℃ C., load 2.16kg) of the component (A2) is 1 to 500g/10 min, and the component (A2) is selected from the group consisting of: (A2-1) a propylene homopolymer, (A2-2) a random copolymer of propylene and an alpha-olefin having 2 or 4 to 8 carbon atoms, (A2-3) a block copolymer of propylene and an alpha-olefin having 2 or 4 to 8 carbon atoms, and combinations thereof.

Description

Polypropylene resin composition containing ultrahigh molecular weight propylene polymer (copolymer)

Technical Field

The present invention relates to a polypropylene resin composition containing an ultrahigh molecular weight propylene polymer (copolymer).

Background

High molecular weight propylene polymers are useful particularly as resin components of extrusion molded articles (plain sheets, foamed sheets, blow molded articles, etc.), and various studies have been made on the production of high molecular weight propylene polymers. For example, patent document 1 discloses a crosslinked ultrahigh molecular weight olefin polymer having an intrinsic viscosity [. eta. ] of 5 to 50dl/g as measured in a decalin solvent at 135 ℃. However, the olefin-based polymer specifically disclosed in the examples is only polyethylene. Patent document 2 discloses an ultrahigh molecular weight propylene homopolymer having an intrinsic viscosity [. eta. ] of 7dl/g or more and less than 25dl/g as measured using a decalin solution. In the examples of this document, a propylene polymer having [ eta ] of 20.2dl/g is disclosed. Patent document 3 discloses an ultrahigh molecular weight polypropylene having an intrinsic viscosity [. eta. ] of at least 5dl/g as measured using a decalin solution. In the examples of this document, polypropylene having [. eta. ] of 20.25dl/g is disclosed. Patent document 4 discloses a polypropylene having an intrinsic viscosity [. eta. ] of 5 to 20dl/g as measured in a tetralin (tetralin) solvent at 135 ℃. Patent document 5 discloses a foam molded from a resin composition containing a propylene polymer (copolymer) having an intrinsic viscosity [. eta. ] measured in a decalin solvent at 135 ℃ of 5 to 20dl/g (claim and paragraph 0018). However, the intrinsic viscosity of the propylene polymer (copolymer) specifically disclosed in patent document 5 is 3.8 to 14.8dl/g (Table 1).

Documents of the prior art

Patent document

Patent document 1 japanese patent No. 5979985

Patent document 2 japanese patent No. 5653761

Patent document 3 japanese patent No. 3023382

Patent document 4 japanese patent No. 6144045

Patent document 5 Japanese patent laid-open publication No. 2013-100491

Summary of The Invention

Problems to be solved by the invention

Patent document 1 does not specifically disclose a propylene polymer having a high [ η ] value. Patent documents 2 and 3 disclose propylene polymers having [. eta. ] of about 20dl/g, and the viscosity is a value measured using decalin as a solvent. It is obvious to those skilled in the art that when the value of [ η ] measured with decalin as a solvent is converted to a value measured with tetralin as a solvent, the value becomes low. Therefore, [ η ] described in patent documents 2 and 3 is less than 20dl/g when it is converted into a value measured using tetralin as a solvent. Similarly, when the intrinsic viscosity described in patent document 5 is converted to a value measured with tetralin as a solvent, it is lower than the original value. As can be seen from the foregoing, compositions containing ultra-high molecular weight propylene polymers having [. eta. ] greater than 20dl/g as measured using tetralin as a solvent have not been reported so far. In view of the above circumstances, an object of the present invention is to provide a composition containing an ultrahigh molecular weight propylene polymer.

Means for solving the problems

The present inventors have found that a composition containing the above-mentioned ultrahigh-molecular-weight polypropylene-based polymer can be produced by optimizing a polymerization catalyst or polymerization conditions, and have completed the present invention. That is, the above problem is solved by the following invention.

[1] A polypropylene resin composition comprising a polypropylene resin and a propylene polymer,

specifically disclosed is a polypropylene resin composition containing 0.1-10% by weight of a component (A1) and 99.9-90% by weight of a component (A2) based on the total amount of the components (A1) and (A2),

the component (A1) is a propylene homopolymer or a copolymer of propylene and 30 wt% or less of an alpha-olefin having 2 or 4 to 8 carbon atoms, and has an intrinsic viscosity of more than 20dl/g as measured in a tetralin solvent at 135 ℃,

the component (A2) has an MFR (230 ℃ C., load of 2.16kg) of 1 to 500g/10 min,

ingredient (a2) is selected from the group consisting of:

(A2-1) propylene homopolymer,

(A2-2) a random copolymer of propylene and an alpha-olefin having 2 or 4 to 8 carbon atoms,

(A2-3) a block copolymer of propylene and an alpha-olefin having 2 or 4 to 8 carbon atoms,

And combinations thereof.

[2] The resin composition according to [1], wherein the α -olefin in the component (A1) is ethylene.

[3] The resin composition according to [2], wherein the intrinsic viscosity of the component (A1) is 23dl/g or more, and the content of ethylene is 3 to 30% by weight.

[4] The resin composition according to [2] or [3], wherein,

the component (A1) is a propylene-ethylene copolymer, and the melting point Tm (. degree.C.) of the copolymer, which is determined by DSC at a temperature rise rate of 10 ℃ per minute, and the ethylene content C2 (wt%) in the copolymer satisfy the following formula (1):

Tm≥-3.4×C2+162...(1)

[5] a method for producing a resin composition according to any one of [1] to [4], comprising the steps of:

using (a) a solid catalyst containing magnesium, titanium, halogen and an electron donor compound as essential components,

(b) An organoaluminum compound,

And (c) a catalyst containing an external electron donor compound, if necessary, and polymerizing the corresponding monomer to prepare the component (A1).

[6] The resin composition according to any one of [1] to [4], which is obtained by a production method comprising a step of polymerizing monomers corresponding to the components (A1) and (A2) in 2 or more polymerization steps performed sequentially or continuously.

[7] The resin composition according to [6], wherein the step of polymerizing the monomer corresponding to the component (A1) comprises a prepolymerization step.

[8] The resin composition according to any one of [1] to [4] and [6] to [7], wherein MFR (230 ℃ C., load 2.16kg) is 1 to 20g/10 min.

[9] The resin composition according to any one of [1] to [4] and [6] to [8], wherein the melt tension (200 ℃, diameter 2.095mm) is 2.5 to 30g by weight.

[10] A foam formed from the resin composition described in any one of [1] to [4] and [6] to [9 ].

Effects of the invention

According to the present invention, there can be provided a composition containing an ultrahigh molecular weight propylene polymer.

Detailed Description

The present invention will be described in detail below. In the present invention, "X to Y" includes the end values X and Y.

1. Composition comprising a metal oxide and a metal oxide

1-1. component (A1)

(1) Intrinsic viscosity

The polypropylene resin composition of the present invention (hereinafter, also simply referred to as "the composition of the present invention") contains, as a component (a1), a propylene homopolymer or a copolymer of propylene and 30% by weight or less of an α -olefin having 2 or 4 to 8 carbon atoms. The component (A1) has an intrinsic viscosity of more than 20dl/g as measured in tetralin solvent at 135 ℃. Intrinsic viscosity is an index of molecular weight, and the component (a1) has an unprecedented extremely high molecular weight. Since the melt tension of the resin composition containing the propylene polymer (copolymer) having a high intrinsic viscosity is also high, the composition of the present invention provides, for example, an excellent foam. From this viewpoint, the lower limit of the intrinsic viscosity is preferably 23dl/g or more. From the viewpoint of ease of production, the upper limit of the intrinsic viscosity is preferably 50dl/g or less.

(2) Comonomer amount

When the component (a1) is a copolymer, the amount of the comonomer is 30% by weight or less. When the amount of the comonomer is larger than this value, the crystallinity of the copolymer is lowered, and the powder properties of the polymer are deteriorated, so that the production is difficult. From this viewpoint, the upper limit of the amount is preferably 25% by weight or less. On the other hand, the lower limit of the amount of the comonomer is not limited, but is preferably 3% by weight or more, and more preferably 5% by weight or more. In the present invention, the amount of comonomer is the amount of the monomer-derived units in the copolymer. The comonomer is alpha-olefin with 2 or 4-8 carbon atoms. Among them, from the viewpoint of reactivity, ethylene, which is an α -olefin having 2 carbon atoms, is preferable as the comonomer. By copolymerizing ethylene, the intrinsic viscosity of the propylene polymer can be further increased. Therefore, in one embodiment, the component (A1) is a copolymer having an intrinsic viscosity of 23dl/g or more and an ethylene content (content ratio of ethylene-derived units) of 3 to 30% by weight.

(3)XI

The component (A1) preferably contains 40% by weight or more of xylene-insoluble matter, more preferably 50% by weight or more of xylene-insoluble matter, still more preferably 60% by weight or more of xylene-insoluble matter, and particularly preferably 70% by weight or more of xylene-insoluble matter (XI). XI is the crystalline component of the propylene (co) polymer. The upper limit of XI is not particularly limited.

(4) Melting Point

The component (A1) preferably has a melting point of 100 ℃ or higher, more preferably 120 ℃ or higher, still more preferably 140 ℃ or higher, and particularly preferably 150 ℃ or higher. The melting point is a temperature at which the amount of heat of fusion due to melting shows a maximum value, which is observed by performing a second scan using DSC. The second scan is performed by heating and melting a sample (resin), cooling and crystallizing the sample, holding the sample at room temperature for 5 minutes, and then heating the sample for the 2 nd time to perform thermal analysis. Specifically, the sample was heated to a temperature not lower than the melting temperature (230 ℃ C.), held at the temperature for 5 minutes, cooled to 30 ℃ at a cooling rate of 10 ℃ C./minute, held for 5 minutes, and then heated to 230 ℃ at a heating rate of 10 ℃ C./minute, and subjected to thermal analysis.

Component (a1) has the following characteristics: the copolymer has a higher melting point than the conventional copolymer, when the kind and content ratio of the comonomer are the same. Particularly, in the case where the component (A1) is a propylene-ethylene copolymer, the Tm (. degree. C.) and the content ratio of ethylene-derived units in the copolymer C2 (wt.%) preferably satisfy formula (1).

Formula (1): tm is not less than-3.4 XC 2+162

1-2. component (A2)

The composition of the present invention contains a polymer having MFR (230 ℃ C., load of 2.16kg) of 1 to 500g/10 min as component (A2). MFR was measured in accordance with JIS K7210-1 under the conditions of a temperature of 230 ℃ and a load of 2.16 kg. When the MFR is larger than the upper limit value, the dispersion of component (A2) is poor, and when it is smaller than the lower limit value, the melt flowability is insufficient. From this viewpoint, the upper limit of MFR is preferably 100g/10 min or less, and the lower limit is preferably 5g/10 min or more. The MFR of component (A1) could not be determined.

The component (A2) is selected from the group consisting of a propylene homopolymer (component (A2-1)), a random copolymer of propylene and an alpha-olefin having 2 or 4 to 8 carbon atoms (component (A2-2)), a block copolymer of propylene and an alpha-olefin having 2 or 4 to 8 carbon atoms (component (A2-3)), and a combination thereof.

As the component (A2-1), known ones can be used. As the component (a2-2), a random copolymer (RACO) of propylene and ethylene is preferred from the viewpoint of productivity. From the viewpoints of rigidity and heat resistance, the content of the α -olefin in the component (a2-2) is preferably 5% by weight or less.

The component (a2-3) may be a polymerization mixture (HECO) obtained by copolymerizing propylene or the above-mentioned α -olefin in the presence of a propylene polymer. From the viewpoint of productivity, ethylene is preferred as the α -olefin (comonomer). From the viewpoint of stable production, the content of the α -olefin in the component (a2-3) is preferably 40% by weight or less. The lower limit is not limited, but is preferably 5% by weight or more from the viewpoint of imparting impact resistance.

The component (A2) may be a combination of 2 or more of the components (A2-1), (A2-2) and (A2-3). In this case, the ratio of each component is not limited, but each component is preferably blended so that the amount of the comonomer in the component (a2) is 40% by weight or less.

1-3. composition

(1) Ratio of component (A1) to component (A2)

The content of the component (A1) is 0.1 to 10% by weight and the content of the component (A2) is 99.9 to 90% by weight based on the total amount of the component (A1) and the component (A2). The composition may be appropriately adjusted depending on the application, but from the viewpoint of ease of production and the like, the upper limit of the content of the component (a1) is preferably 8 wt% or less, and more preferably 6 wt% or less. The lower limit is preferably 0.2% by weight or more, more preferably 0.5% by weight or more, and still more preferably 1% by weight or more. When the proportion is less than 0.1% by weight, the effect brought about by the component (a1) is difficult to obtain, and when it is more than 10% by weight, the fluidity of the composition may deteriorate.

(2) Other ingredients

The composition of the present invention may further contain conventional additives usually used for olefin polymers such as blowing agents, antioxidants, chlorine absorbers, heat stabilizers, light stabilizers, ultraviolet absorbers, internal lubricants, external lubricants, antiblocking agents, antistatic agents, antifogging agents, crystal nucleating agents, flame retardants, dispersants, copper inhibitors, neutralizers, plasticizers, crosslinking agents, peroxides, oil-extended and other organic and inorganic pigments. The additive amount of each additive may be a known amount. The blowing agent will be described later.

The resin composition of the present invention may contain thermoplastic elastomers such as olefin elastomers, styrene elastomers, vinyl chloride elastomers, polyurethane elastomers, ester elastomers, and amide elastomers, as long as the effects of the present invention are not impaired. The number of the elastomers may be only 1, or may be 2 or more. When the elastomer is contained, the content thereof may be a known amount, but is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, relative to 100 parts by weight of the total amount of the component (a1) and the component (a2) (hereinafter, also referred to as "resin component").

Further, the composition of the present invention may contain a filler as needed within a range not to impair the effects of the present invention. The filler is added mainly for the purpose of improving the rigidity of the molded body. Examples of the filler include inorganic fillers such as talc, clay, calcium carbonate, magnesium hydroxide, and glass fiber, and organic fillers such as carbon fiber and cellulose fiber. These fillers may be used alone in 1 kind, or may be used in combination in 2 or more kinds. In order to improve the dispersibility of the filler, surface treatment of the filler or preparation of a master batch of the filler and the resin may be performed as necessary. Among the fillers, talc is preferable from the viewpoint of being easily mixed with the polypropylene resin and easily improving the rigidity of the molded article. The amount of each filler added may be a known amount. For example, it may be 0.1 to 40 parts by weight relative to 100 parts by weight of the resin component.

1-4. Properties

(1)MFR

The resin composition of the present invention preferably has an MFR (230 ℃ C., load of 2.16kg) of 1 to 20g/10 min, more preferably 2 to 15g/10 min.

(2) Melt tension

The lower limit of the melt tension of the resin composition of the present invention is preferably 2.5g or more, more preferably 4.0g or more, and even more preferably 5.0g or more, from the viewpoint of suppressing the collapse of foam during foam molding, maintaining the closed cell property of the foam, and maintaining the appearance. Since the upper limit of the intrinsic viscosity is preferably 50dl/g or less, the upper limit of the melt tension is preferably 30g or less in weight from the viewpoint of ease of production. Generally, in a polypropylene resin composition, the larger the MFR, the smaller the melt tension, but when the balance between MFR and melt tension is within a specific range, the foam moldability of the polypropylene resin composition is improved. The balance between MFR and melt tension can be indicated by the product of log (MFR +1) and log (M T) using MFR (230 ℃, load 2.16kg, unit g/10 min) and melt tension (M T) (200 ℃, diameter 2.095mm, unit g weight). In the present invention, the product of log (MFR +1) and log (m T) is preferably 0.40 or more, more preferably 0.45 or more, and still more preferably 0.50 or more. In the present invention, the melt tension is the tension at which the composition of the present invention is extruded at 200 ℃ from a hole having a diameter of 2.095mm at a speed of 15 mm/min, and a strand of the molten composition is pulled at a speed of 6.5 m/min.

2. Manufacturing method

The composition of the present invention can be produced by a known method such as melt kneading or solution mixing of the component (a1) and the component (a2), or polymerization mixing by multistage polymerization. Further, the composition may be used as a master batch and combined with other polyolefins to form a secondary composition.

Preferably, the composition of the present invention is manufactured by the following method.

The method comprises the following steps: a method comprising a step of polymerizing monomers corresponding to the components (A1) and (A2) in 2 or more polymerization steps performed sequentially or continuously

The method 2 comprises the following steps: a method of preparing a composition containing the component (A1) at a high concentration and diluting the composition with the component (A2) as a master batch

The method 3 comprises the following steps: method for separately preparing component (A1) and component (A2) and mixing them

The method 4 comprises the following steps: a method of polymerizing and mixing the component (A1) and the component (A2) using a polymerizer having a gradient with respect to the monomer concentration or the polymerization conditions (for example, the method described in JP-A-2002-520426)

In the present invention, the methods of methods 1 to 3 are more preferably used, and will be described below.

2-1. production method having 2 polymerization steps (method 1)

The method comprises a step of polymerizing monomers corresponding to the components (A1) and (A2) in 2 or more polymerization steps performed sequentially or continuously. In particular, it is preferable to use a method of producing a polymer of the component (a1) by polymerizing a raw material monomer of the component (a) and polymerizing the raw material monomer of the component (a2) in the presence of the polymer. The polymerization can be carried out in the liquid phase, in the gas phase or in the liquid-gas phase. Chain transfer agents (e.g., hydrogen or ZnEt) may be used₂) And the like, commonly used molecular weight regulators known in the art.

In particular, the process preferably comprises a step of a prepolymerization process as one of the reaction stages. The prepolymerization refers to a step of forming a polymer chain as a main polymerization endpoint of the subsequent raw material monomer in the solid catalyst component. The prepolymerization can be carried out by a known method. The prepolymerization is usually carried out at 40 ℃ or lower, preferably at 30 ℃ or lower, more preferably at 20 ℃ or lower. The prepolymerized catalyst (prepolymerized catalyst) is introduced into the polymerization reaction system and used for the main polymerization of the raw material monomers. In the present invention, the ultrahigh molecular weight component (a1) can be synthesized in the preliminary polymerization step, and the component (a2) can be subjected to main polymerization using the preliminary polymerization catalyst. By such polymerization, the dispersibility of the component (a1) in the component (a2) can be improved.

The main polymerization may be carried out by introducing the monomer at one time, or may be carried out by introducing the monomer with a time difference. The monomer used for the main polymerization is generally a monomer corresponding to the component (A1) and the component (A2). However, as described above, in the case where the component (a1) is obtained by prepolymerization, only the monomer corresponding to the component (a2) may be supplied in the main polymerization. The polymerization may be carried out in the liquid phase, the gas phase, or the liquid-gas phase. The polymerization temperature is preferably 0 to 90 ℃, more preferably 20 to 80 ℃. In the case of carrying out in the liquid phase, the polymerization pressure is preferably in the range of 0.8 to 6.0MPa, and in the case of carrying out in the gas phase, it is preferably in the range of 0.5 to 3.0 MPa. Chain transfer agents (e.g., hydrogen or ZnEt) may be used in minor amounts₂) And the like, commonly used molecular weight regulators known in the art.

Any catalyst can be used for the polymerization of the component (a 2). On the other hand, in order to obtain an ultrahigh molecular weight polymer, in the polymerization of the component (a1), it is preferable to use (a) a solid catalyst containing magnesium, titanium, halogen and an electron donor compound as essential components, (b) an organoaluminum compound, and if necessary (c) a catalyst containing an external electron donor compound. The catalyst will be described later.

2-2. method of diluting composition having high concentration of component (A1) (method 2)

The composition of the present invention can also be obtained by preparing a composition containing the component (a1) at a high concentration by the above-mentioned method and diluting the composition with the component (a2) as a master batch. In the composition containing the component (a1) at a high concentration, the content of the component (a1) may be in the range of 0.1 to 10% by weight, or may be more than the upper limit. However, the content of the component (A1) in the composition obtained after dilution is 0.1 to 10% by weight. As the dilution method, a known method such as dry blending or melt kneading in an extruder can be used.

[ catalyst ]

(1) Solid catalyst (component (a))

The component (a) can be produced by a known method, for example, by contacting a magnesium compound, a titanium compound and an electron donor compound with each other. As the titanium compound used in the production of the component (a), preferred is a compound represented by the general formula: ti (OR)_gX_4-gA tetravalent titanium compound. Wherein R is alkyl, X is halogen, and g is not less than 0 and not more than 4. More specifically, TiCl may be mentioned as the titanium compound₄、TiBr₄、TiI₄Titanium tetrahalides; ti (OCH)₃)Cl₃、Ti(OC₂H₅)Cl₃、Ti(O_n-C₄H₉)Cl₃、Ti(OC₂H₅)Br₃、Ti(OisoC₄H₉)Br₃Titanium trihalides; ti (OCH)₃)₂Cl₂、Ti(OC₂H₅)₂Cl₂、Ti(O_n-C₄H₉)₂Cl₂、Ti(OC₂H₅)₂Br₂Titanium alkoxides dihalides, etc.; ti (OCH)₃)₃Cl、Ti(OC₂H₅)₃Cl、Ti(O_n-C₄H₉)₃Cl、Ti(OC₂H₅)₃Trialkoxytitanium monohalides such as Br; ti (OCH)₃)₄、Ti(OC₂H₅)₄、Ti(O_n-C₄H₉)₄And tetraalkoxytitanium, and the like. Among them, preferred are halogen-containing titanium compounds, particularly titanium tetrahalides, and particularly preferred is titanium tetrachloride.

Examples of the magnesium compound include magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond, such as dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, dipentylgagnesium, dihexylmagnesium, didecylmagnesium, ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride, pentylmagnesium chloride, butylethoxymagnesium, ethylbutylmagnesium, and butylmagnesium hydride. These magnesium compounds may be used in the form of a complex compound such as organoaluminum, and may be in the form of a liquid or solid. More preferred examples of the magnesium compound include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, and octoxy magnesium chloride; allyloxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; magnesium alkoxides such as magnesium ethoxide, magnesium isopropoxide, magnesium butoxide, magnesium n-octoxide and magnesium 2-ethylhexoxide; dialkoxymagnesiums such as dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium; allyloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium.

The electron donor compound is generally referred to as "internal electron donor compound". In the present invention, as the internal electron donor compound, a compound having an ester skeleton represented by the formula (I) is preferable.

[ chemical formula 1]

Wherein R1 is independently a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms. The hydrocarbon group may have a heteroatom such as halogen or P, S, N, O, Si, or may form a ring. R2 is as defined for R1, but R2 and R1 do not necessarily have the same structure. Further, R1 and R2 may be linked to form a ring.

A is a divalent crosslinking group. The chain length between the cross-links is preferably 1 to 10 atoms. When a has a cyclic structure, the chain length means the number of atoms having the shortest sequence between oxygen atoms bonded to a. A is preferably represented by- (ZR)³ _m)_n-. Z is preferably C, Si, Ge, O, N, S or P. R³Each independently hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, may contain the above-mentioned hetero atom, and may further contain a plurality of R³Fuse and form more than 1 loop. m is a number corresponding to the valence of Z, and n is an integer of 1 to 10. For example, R³May form an aromatic ring, a heterocyclic ring or an alicyclic ring together with Z. In- (ZR)³ _m)_nO, S and N are not directly bonded to the oxygen atom of formula (I).

In the present invention, it is more preferable to use a urethane-based compound as the internal electron donor compound. The carbamate compound is a compound having a carbamate skeleton and is represented by formula (II).

[ chemical formula 2]

Wherein R4 is independently a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms. The hydrocarbon group may have a heteroatom such as halogen or P, S, N, O, Si, and 2R 4 may be linked to form a ring. R5 is as defined for R4, but R4 and R5 do not necessarily have the same structure.

A is as defined above, and Z is preferably C or Si, more preferably C. In particular, compounds having the following combinations are preferred.

A: a divalent aromatic group which may have a substituent. Examples of the aromatic group include phenylene and naphthylene. Examples of the substituent include a linear or branched alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group.

R4, R5: a straight-chain or branched alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group.

Specifically, as the compound defined in formula (II), a compound described in the specification of U.S. patent application No. 2015/0266981 can be used.

(2) Organoaluminum Compound (component (b))

Examples of the organoaluminum compound include the following compounds.

Trialkylaluminums such as triethylaluminum and tributylaluminum;

trienyl aluminum such as triisopentadienyl aluminum:

dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide;

alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxy and butylaluminum sesquibutanol;

partially halogenated alkylaluminums such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, diethylaluminum chloride, dipropylaluminum chloride and dibutylaluminum chloride;

dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride;

partially hydrogenated alkylaluminums such as ethylaluminum dihydride and propylaluminum dihydride;

partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxide chloride, butylaluminum butoxide chloride, ethylaluminum ethoxide bromide, and the like.

(3) Electron donor Compound (component (c))

This electron donor compound is also referred to as "external electron donor compound". The external electron donor compound is preferably an organosilicon compound, and specific examples thereof include the following compounds.

Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-triyldimethoxysilane, bis-m-triyldimethoxysilane, bis-p-triyldiethoxysilane, bis-ethylphenyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, diphenylmethyldimethoxysilane, diphenyldimethoxysilane, di-o-t-butylmethyldimethoxysilane, di-m-t-butylmethyldimethoxysilane, di-t-ethyldimethoxysilane, di-t-ethyltriethoxysilane, di-ethyltrimethoxysilane, di-ethoxysilane, di-ethyldimethoxysilane, di-t-ethyltrimethoxysilane, n-ethyltriethoxysilane, n-propyltriethoxysilane, n-ethyltriethoxysilane, n-ethyltrimethoxysilane, n-methyldimethoxysilane, n-butylmethyldimethoxysilane, n-dimethyldimethoxysilane, n-butylmethyldimethoxysilane, n-butyldimethoxysilane, n-butylmethyldimethoxysilane, n-butyldimethoxysilane, n-butylmethyldimethoxysilane, n-butyldimethoxysilane, n-butylmethyldimethoxysilane, n-butyldimethoxysilane, n-butylmethyldimethoxysilane, n-butyldimethoxysilane, n-, Decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, gamma-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, tolyltrimethoxysilane, n-butyltriethoxysilane, isobutyltriethoxysilane, phenyltriethoxysilane, gamma-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornantrimethoxysilane, 2-norbornantriethoxysilane, 2-norbornanmethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltrialkoxysilane, gamma-chloropropyltrimethoxysilane, ethyltriethoxysilane, butyltrimethoxysilane, trimethylphenoxysilane, methyltrialkoxysilane, butyltrimethoxysilane, or a mixture of, Vinyltris (. beta. -methoxyethoxysilane), vinyltriacetoxysilane, dimethylethylenedisiloxane, methyl (3,3, 3-trifluoro-n-propyl) dimethoxysilane, cyclohexylethyldimethoxysilane, cyclopentyl-t-butoxydimethoxysilane, diisobutyldimethoxysilane, isobutylisopropyldimethoxysilane, n-propyltrimethoxysilane, di-n-propyldimethoxysilane, tolyltrimethoxysilane, t-butylethyldimethoxysilane, t-butylpropyldimethoxysilane, t-butyl-t-butoxydimethoxysilane, isobutyltrimethoxysilane, cyclohexylisobutyldimethoxysilane, di-sec-butyldimethoxysilane, isobutylmethyldimethoxysilane, bis (decahydroisoquinolin-2-yl) dimethoxysilane, dimethyltriethoxysilane, dimethylmethyldimethoxysilane, dimethyltrimethoxysilane, dimethylmethyldimethoxysilane, dimethyltrimethoxysilane, dimethylmethyldimethoxysilane, dimethyldimethoxysilane, dimethyltrimethoxysilane, dimethyldimethoxysilane, dimethyltrimethoxysilane, dimethylmethyldimethoxysilane, dimethyldimethoxysilane, dimethyltrimethoxysilane, dimethyldimethoxysilane, dimethyltrimethoxysilane, dimethyldimethoxysilane, dimethyltrimethoxysilane, dimethyldimethoxysilane, dimethyltrimethoxysilane, and the mixture thereof, dimethyltrimethoxysilane, dimethyldimethoxysilane, and the mixture thereof, Diethylaminotriethoxysilane, dicyclopentyl-bis (ethylamino) silane, tetraethoxysilane, tetramethoxysilane, isobutyltriethoxysilane.

(4) Composition ratio

The composition ratio of the components (a) to (c) is not limited, but the composition ratio of the components (a) and (b) is adjusted so that the molar ratio of Al/Ti is preferably 10 to 1000, more preferably 30 to 600. When the component (c) contains silicon, the composition ratio of the components (a) and (c) is adjusted so that the Si/Al molar ratio is preferably 0.01 to 1.5, more preferably 0.05 to 1.0.

(5) Polymerisation

The raw material monomers were contacted with the catalyst prepared as described above and polymerized. In this case, as described above, first, the catalyst may be used for preliminary polymerization.

2-3. method for separately preparing and mixing component (A1) and component (A2) (method 3)

In method 3, the component (a1) and the component (a2) prepared by an arbitrary method are mixed with other components as necessary. The order of addition of the components is not limited. The mixing method is not particularly limited, and examples thereof include a method using a mixer such as a henschel mixer or a tumbler mixer. The mixture obtained by mixing may be melt-kneaded and then granulated. In the present invention, from the viewpoint of uniformly dispersing the high molecular weight component, it is preferable to include a step of granulating by melt kneading. The method of melt-kneading is not particularly limited, and for example, a melt-kneading apparatus such as a single-screw extruder, a twin-screw extruder, a banbury mixer, a kneader, a roll mill, or the like can be used.

3. Use of

The composition of the present invention has a high melt tension and die swell because it contains the ultra-high molecular weight component (A1). Therefore, the composition of the present invention is useful for applications to extrusion molded articles (plain sheets, foamed sheets, blow molded articles, etc.) or injection molded articles. The composition of the present invention may be a composition using a crystalline and hardly soluble component (a1) such as an organic filler. The composition of the invention may also be used as a masterbatch and combined with other polyolefins to make a secondary composition. The secondary composition also preferably has the MFR and melt tension described above. In the secondary composition, the mixing weight ratio of the composition of the present invention to other polyolefin is not limited, and may be 100: (10-100). As the other polyolefin, known polyolefins such as propylene polymers (propylene homopolymers other than the component (a2), propylene copolymers (RACO), polymerization mixtures (HECO)), ethylene polymers, and the like can be used.

(1) Foamable composition

The composition of the present invention is useful as a foamable composition. Next, a blowing agent usable for the foamable composition will be described. As the foaming agent, any of a decomposition type foaming agent and a solvent type foaming agent can be used. The decomposition type foaming agent is a compound which decomposes under a cylinder temperature condition of a molding machine to generate a gas such as carbon dioxide or nitrogen. As the decomposition type foaming agent, any of inorganic type and organic type can be used. Further, a known foaming aid such as an organic acid for promoting gas generation may be used in combination.

Examples of the inorganic decomposition type foaming agent include sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite, citric acid, and sodium citrate. Examples of the organic decomposition type foaming agent include N-nitroso compounds such as N, N '-dinitrosoterephthalamide and N, N' -dinitrosopentamethylenetetramine; azo compounds such as azodicarbonamide, azobisisobutyronitrile, azocyclohexanecarbonitrile, azodiaminobenzene, and barium azodicarboxylate; sulfonyl hydrazide compounds such as benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p '-oxybis (benzenesulfonyl hydrazide), diphenylsulfonyl hydrazide-3, 3' -disulfonyl hydrazide and the like; azides such as calcium azide, 4' -diphenyldisulfonylazide and p-toluenesulfonylazide, and the like.

Among these blowing agents, when an inorganic decomposition type blowing agent is used, a carbonate or a hydrogen carbonate such as sodium hydrogen carbonate is preferable from the viewpoint of less influence on the environment, safety, and stability of the foaming unit, and in this case, an organic carboxylic acid may be used in combination as the foaming aid.

The solvent type foaming agent is injected from a cylinder part of a molding machine into a composition containing no foaming agent, and evaporates in a mold to function as a foaming agent. Low boiling point aliphatic hydrocarbons such as propane, butane, neopentane, heptane, isoheptane, isohexane, and hexane, low boiling point fluorocarbons such as freon, and the like can be used. Alternatively, an inert gas such as nitrogen or carbon dioxide may be pressurized and used as a blowing agent for the supercritical fluid.

The foaming agent used in the foamable composition may be added in the form of a foaming agent masterbatch using polyolefin as a carrier. Examples of the polyolefin include polypropylene, polyethylene, and polystyrene. The carrier contained in the master batch corresponds to the aforementioned other ingredients. The content of the decomposition type foaming agent or solvent type foaming agent contained in the foaming agent master batch is usually 5 to 50% by weight, preferably 10 to 40% by weight, and commercially available products can be used as they are.

The amount of the foaming agent added to the composition of the present invention is usually 1 to 10phr, preferably 2 to 6phr, and more preferably 2 to 4 phr. Further, the optimum amount is selected within this range by taking into account the amount of generated gas, expansion ratio, and the like. The expansion ratio is preferably 1.5 times or more, more preferably 2.0 times or more, and still more preferably 2.5 times or more. The foamable composition within this range gives a foam having uniform cell diameters and uniformly dispersed cells.

(2) Used as a master batch

As described above, the composition of the present invention may be used as a master batch and combined with a polyolefin other than the components (A1) and (A2) to prepare a secondary composition. As the polyolefin other than the components (A1) and (A2), any polyolefin can be used.

[ examples ]

[ example 1]

1) Polypropylene resin composition

In a 300mL four-necked round bottom flask purged with nitrogen,45mL of toluene and 10.0g of fine spherical Mg (OC) were introduced at 5 ℃₂H₅)₂. 28.7ml of titanium tetrachloride was added dropwise over 10 minutes with stirring, and 11.3 mmol of 5 (tert-butyl) -3-methyl-1, 2-phenylenebis (diethyl carbamate) (hereinafter also referred to as compound a) was added. The temperature was raised to 110 ℃ and held for 120 minutes. Then, the stirring was stopped, the solid product was allowed to settle, and the supernatant liquid was aspirated. Then, it was washed 4 times with toluene (75mL) at 90 ℃.

To the washed solid was added 50ml of toluene. To this was added 21ml of titanium tetrachloride, and after the temperature was raised to 100 ℃, the mixture was stirred for 90 minutes. Then, the stirring was stopped, the solid product was allowed to settle, and the supernatant liquid was aspirated. Next, the column was washed 6 times with heptane (75mL) at 40 ℃. The washed solid was dried under reduced pressure to obtain 7.6g of a solid catalyst component (a). The solid catalyst component contained 14.3 wt% of compound a, 14.0 wt% of Mg, and 4.0 wt% of Ti.

[ front-end polymerization ]

The autoclave with a stirrer, which had an internal volume of 20L, was sufficiently vacuum-dried in a reactor and replaced with nitrogen. 59.3mg of the solid catalyst component containing the prepared compound a, Triethylaluminum (TEAL) and Dicyclopentyldimethoxysilane (DCPMS) were added in an amount such that the molar ratio of Al/Ti was 150 and the molar ratio of Si/Al was 1.0. Next, 5.6kg of liquefied propylene was charged into the reactor while continuously supplying ethylene gas during the polymerization, and polymerization was carried out at 40 ℃ for 10 minutes while adjusting the ethylene partial pressure to be constant. The propylene-ethylene copolymer (component (a1)) of the present invention is obtained by adjusting the polymerization pressure. Then, the unreacted monomers were purged and the inside of the reaction vessel was sufficiently replaced with nitrogen.

(latter polymerization)

Then, TEAL and DCPMS were added to the reactor in such an amount that the molar ratio of Al/Ti was 400 and the molar ratio of Si/Al was 0.05. 5.6kg of liquefied propylene and hydrogen were added so that the hydrogen concentration in the liquid propylene was 0.7 mol%, the temperature of the autoclave was raised to 70 ℃ and polymerization (propylene polymerization) was carried out for 180 minutes. After the polymerization was completed, the unreacted monomers were purged to obtain 4.6kg of a powdery composition. This composition is a polymerized composition obtained by polymerizing and mixing the propylene-ethylene copolymer of the present invention (component (a1)) and polypropylene (component (a 2)). The physical properties and the like of this composition are shown in Table 1. However, the intrinsic viscosity, the content ratio of ethylene-derived units, and the melting point of the propylene-ethylene polymer (copolymer) of the present invention are the results of analysis of the polymer obtained by the preceding-stage polymerization under the same conditions. In the composition, the ratio of the propylene-ethylene polymer (copolymer) of the present invention is determined from the activity ratio to the former-stage polymerization.

To the powdery polymerization composition obtained above, 0.2phr of B225 manufactured by BASF corporation as an antioxidant and 0.1phr of calcium stearate manufactured by southern chemical industries, Ltd as a neutralizing agent were added, and the mixture was stirred for 1 minute by a Henschel mixer to obtain a mixture. Then, the mixture was melt-kneaded using an extruder (a co-rotating twin-screw extruder having a screw diameter of 15mm, manufactured by Technovel, Ltd.) with a screw temperature of 230 ℃. Next, the melted mixture was discharged from the extruder, cooled to form a strand, and after the strand was cut, the composition (a) was obtained in the form of pellets.

2) Formation of foam

To the granular composition (A) obtained as described above, 4phr of CELLMIC MB3064 manufactured by Sanko Co., Ltd was added as a foaming agent, and dry-blended to obtain a foamable composition. Next, using this foamable composition, a foamed strand was formed under the following conditions, and the obtained foam was evaluated.

An extruder: single-shaft extruder TP-15 manufactured by Thermo Plastics industries Co., Ltd

Shape of the mold part: wire drawing die

Size of the mold part: 2mm phi

Extrusion amount: 500g/h

Screw shape: full-thread screw

Screw rotation speed: 40rpm

Setting temperature of the charging barrel: 210 deg.C

Setting temperature of the mold part: 180 deg.C

Similarly, to the granular composition (A) obtained in 1), 6phr of CELLMIC MB3064 manufactured by Sanko chemical Co., Ltd was added as a foaming agent, and dry-blended to obtain a foamable composition. As described above, a foam was obtained by using the foamable composition, and evaluated.

Similarly, the granulated composition (A) obtained in 1) was hot-pressed at 230 ℃ to obtain a non-expandable sheet (thickness: 500 μm). The test piece was cut to prepare a test piece, and the rigidity was measured. These results are shown in table 1.

[ examples 2 to 5]

Polymerization was carried out in the same manner as in example 1 except that the ethylene partial pressure in the former stage polymerization, the hydrogen concentration in the latter stage polymerization and the polymerization time were changed, to obtain composition (a) shown in table 1. However, in example 4, the former-stage polymerization was carried out with the ethylene partial pressure set to zero, that is, without supplying ethylene gas. Using these compositions (A), foams and non-foamed sheets were obtained in the same manner as in example 1 and evaluated. These results are shown in table 1.

Comparative example 1

Polymerization was carried out in the same manner as in example 4 except that the molar ratio of Al/Ti was changed to 500 and the molar ratio of Si/Al was changed to 0.1 in the former polymerization, and the hydrogen concentration and polymerization time in the latter polymerization were adjusted, to obtain composition (a) shown in table 1. In addition, when the molar ratio of Al/Ti is changed, the amount of TEAL to be used is increased.

Comparative example 2

MgCl was prepared by the method described in example 1 of European patent No. 674991₂A solid catalyst on which Ti and diisobutylphthalate as an internal electron donor compound are supported, and a solid catalyst for polymerization. Next, the solid catalyst was contacted with TEAL and Cyclohexylmethyldiethoxysilane (CHMMS) at-5 ℃ for 5 minutes in such an amount that the subsequent weight ratio of TEAL to solid catalyst was 8 and the weight ratio of TEAL/CHMMS to solid catalyst was 6.5. The obtained catalyst system was kept in suspension in liquid propylene at 20 ℃ for 5 minutes, thereby carrying out prepolymerization. Subjecting the obtained prepolymerizationAfter the introduction of the product into a polymerization reactor, hydrogen and propylene were supplied to the reactor, and the polymerization temperature and the hydrogen concentration were set to 75 ℃ and 0.04 mol%, respectively, to produce a propylene homopolymer. To the obtained polymer, 0.2% by weight of B225 produced by BASF corporation as an antioxidant and 0.05% by weight of calcium stearate produced by shinan chemical industry co., ltd.was blended as a neutralizing agent, and the blend was stirred and mixed for 1 minute by a henschel mixer, and then extruded at a cylinder temperature of 230 ℃ by a uniaxial extruder (NVC produced by meson mechanical corporation) having a screw diameter of 50mm, and after cooling the strand in water, the strand was cut by a pelletizer, thereby obtaining a granular polypropylene resin composition (a) consisting of only the component (a 2)).

Comparative example 3

The solid catalyst component was prepared according to the preparation method described in the example of Japanese patent application laid-open No. 2011-500907. Specifically, a solid catalyst component was prepared in the following manner.

Into a 500mL four-necked round-bottomed flask purged with nitrogen, 250mL of TiCl was introduced at 0 ℃₄. While stirring, 10.0g of finely spherical MgCl was added₂·1.8C₂H₅OH and 9.1 mmol of diethyl-2, 3- (diisopropyl) succinate. MgCl₂·1.8C₂H₅OH was produced by the method described in example 2 of U.S. Pat. No. 4,399,054, wherein the rotation speed was changed from 10000rpm to 3000 rpm. The temperature was raised to 100 ℃ and maintained for 120 minutes. Then, the stirring was stopped, the solid product was allowed to settle, and the supernatant liquid was aspirated. Next, the following operation was repeated 2 times to obtain a solid catalyst.

250mL of fresh TiCl were added₄The mixture was allowed to react at 120 ℃ for 60 minutes, and the supernatant liquid was aspirated. The solid was washed 6 times with anhydrous hexane (6X 100mL) at 60 ℃.

The solid catalyst was contacted with TEAL and DCPMS in an amount such that the weight ratio of TEAL to the solid catalyst was 18 and the weight ratio of TEAL/DCPMS was 10 at room temperature for 5 minutes. The obtained catalyst system was kept in suspension in liquid propylene at 20 ℃ for 5 minutes, thereby carrying out prepolymerization. The obtained prepolymer was introduced into a polymerization reactor of stage 1 to obtain a propylene homopolymer, and after unreacted monomers were removed, the obtained polymer was introduced into a polymerization reactor of stage 2 to obtain a copolymer (ethylene-propylene copolymer). In the polymerization, the temperature and pressure were adjusted and hydrogen was used as a molecular weight regulator. The polymerization temperature and the ratio of the reactants were 70 ℃ and 0.90 mol% for the polymerization temperature and the hydrogen concentration in the first stage reactor, and 80 ℃, 0.01 mol% and 0.25 mol% for the polymerization temperature, the hydrogen concentration and C2/(C2+ C3) in the second stage reactor, respectively. Further, the residence times of the first stage and the second stage were adjusted so that the amount of the copolymer component was 30% by weight. Using the obtained propylene-ethylene block copolymer, a polypropylene resin composition (a)) in the form of pellets was obtained in the same manner as in comparative example 2. The MFR and the content ratio of ethylene-derived units of the obtained composition (A) were 10g/10 min and 9.0 wt%, respectively, and the intrinsic viscosity of a polymer soluble in xylene at 25 ℃ obtained by the method described later (corresponding to the component (A1)) was 7 dl/g.

Using the composition (A) obtained in comparative example, a foam and a non-foamable sheet were obtained in the same manner as in example 1 and evaluated. These results are shown in table 1. Foam formation was attempted for the compositions of comparative examples 1 and 2, but foams satisfying the evaluation could not be obtained.

[ example 6]

50% by weight of the composition (A) containing no blowing agent prepared in example 2 and 50% by weight of polypropylene (PX600N, manufactured by SunAllomer K.K.) were dry-blended, and melt-kneaded using an extruder (manufactured by Technovel, Inc., having a screw diameter of 15mm, co-rotating twin-screw extruder) with a screw temperature of 230 ℃ to prepare a composition (A + B)). To this composition, 4phr of CELLMIC MB3064 manufactured by Sanko corporation was added as a foaming agent to prepare a foamable composition. In table 2, the composition (a) prepared in example 2 was labeled as component (a), and the polypropylene was labeled as component (B). Using the foamable composition, a foam and a non-foamable sheet were produced in the same manner as in example 1, and evaluated. Further, a foam in which the amount of the foaming agent was changed to 6phr was produced and evaluated. These results are shown in table 2.

[ example 7]

Foamed and non-foamed sheets were produced and evaluated in the same manner as in example 6, except that the ratio of the component (a) to the component (B) was changed as shown in table 2. These results are shown in table 2.

[ example 8]

Foams and non-foamable sheets were produced and evaluated in the same manner as in example 6, except that the component (a) was changed to the component prepared in example 3. These results are shown in table 2.

[ example 9]

Foams and non-foamed sheets were produced and evaluated in the same manner as in example 6, except that the component (a) was changed to the component prepared in example 1 and the component (B) was changed to the composition (a) of comparative example 3.

These results are shown in table 2.

As shown in tables 1 and 2, the foam obtained from the composition of the present invention is excellent in appearance and closed cell property.

Evaluation was carried out as follows.

[ content ratio of ethylene-derived units ]

A sheet having a thickness of 0.4mm was prepared by hot-pressing a propylene polymer (copolymer) sample at 230 ℃, an IR spectrum of the sample against an air background was collected by Fourier transform infrared spectroscopy (FT-IR), and 760cm to 690cm after correcting the thickness of the sheet was used^-1The content ratio (% by weight) of the ethylene-derived unit in the propylene polymer (copolymer) was determined. The data acquisition parameters are as follows.

Apodization: cosine

Resolution ratio: 2cm^-1

[ Polymer XI ]

The polymer (0.5-1.5 g) was dissolved in 250mL of xylene at 135 ℃ with stirring. After 30 minutes, the solution was cooled to 25 ℃ with stirring and then allowed to stand for 30 minutes. The precipitate was filtered with filter paper, the solution was evaporated in a nitrogen stream and dried under vacuum at 80 ℃ until the residue reached constant weight. Thus, the weight% of polymer soluble in xylene at 25 ℃ was calculated. The amount of xylene-insoluble matter (weight% of insoluble polymer in xylene at 25 ℃, XI) can be determined from 100- "weight% of soluble polymer" and can be considered as the amount of crystalline component in the polymer.

[ intrinsic viscosity of Polymer ]

A sample of a propylene polymer (copolymer) was dissolved in tetralin at 135 ℃ to obtain a solution having a concentration of 0.01 to 0.02 wt%. Using this solution, intrinsic viscosity was measured using a capillary automatic kinematic viscosity measuring apparatus (SS-780-H1, manufactured by Chaishan scientific instruments, Ltd.).

[ melting Point of Polymer ]

The melting point of the polymer was measured by performing the second scan defined as described above using a diamond DSC manufactured by Perkin Elmer.

[MFR]

To 5g of a powdery polymer or a polymer composition, 0.05g of H-BHT manufactured by Kyowa chemical industries, Ltd was added, and the mixture was homogenized by dry blending, and then measured at 230 ℃ under a load of 2.16kg according to JIS K7210-1. The melt-kneaded pellets were measured according to JIS K7210-1 at a temperature of 230 ℃ and a load of 2.16 kg.

[ melt tension ]

The resin composition was melted at a temperature of 200 ℃ using a capillary rheometer (Capillogray 1D, manufactured by Toyo Seiki Seisaku-Sho Ltd.) equipped with a cylindrical orifice having a length of 8.0mm and a diameter of 2.095mm and a flat upper surface. The molten resin composition was discharged from the orifice at a resin extrusion rate of 15 mm/min to form a strand. The strand was pulled at a pulling speed of 6.5 m/min using a rotating pulling device, and the melt tension (melt tension in g weight) was measured.

[ appearance of foam ]

The appearance of the foamed strand foamed to 3.0 times or more and 3.4 times or less was evaluated according to the following criteria.

A: the surface is smooth and the wire is linear

B: the surface being slightly concave or convex

C: the surface has concave-convex and the wire material has undulation

[ independent air bubble Property ]

The foamed strand foamed to 3.0 times or more and 3.4 times or less was cut into a length of 4cm with a razor, one of the strands was immersed in an ethanol solution of a pigment for 30 seconds, and the independent foamability was evaluated by the distance from the cut surface to the inside where ethanol was most impregnated (maximum coloring distance).

A: maximum coloring distance of 2mm or less

B: the maximum coloring distance is more than 2mm and less than 20mm

C: maximum coloring distance greater than 20mm

[ rigidity ]

Stamping the non-foamed sheet into: the length was 2.75 inches and the width was 1.5 inches, and 5 test pieces were prepared.

For each test piece, the rigidity was measured at room temperature of 23 ℃ in accordance with JIS P8125 using a V-5 rigidity tester (model 150-B) manufactured by Taber Instruments Corporation. The measurement conditions at this time are as follows.

Measurement range: 50-500

Range weight: 500 units

Warpage angle: 15 degree

Measuring the span: 5cm

Zooming magnification: 5 times of

Holding time 1 minute

Measuring temperature: 23 deg.C

For each test piece, the values of the right and left warpage angles of 15 ° were read, and the rigidity was determined by averaging them. Then, the rigidity of the non-foamed sheet was determined by the following equation.

E＝9.83×T_su/t³

(E: sheet rigidity [ MPa ]]，T_su: average value of rigidity [ gf cm ]]And t: thickness of test piece [ mm ]])

The larger the value of rigidity, the higher the rigidity is.

It is apparent that in the examples in which the polypropylene resin composition containing 0.1 to 10% by weight of the component (A1) having an intrinsic viscosity of more than 20dl/g as measured in a tetralin solvent at 135 ℃ was obtained, a foam having high rigidity and excellent properties was provided.

Claims

1. A polypropylene resin composition comprising a polypropylene resin and a propylene polymer,

the polypropylene resin composition comprises the following components (A1) and (A2), wherein the content of the component (A1) is 0.1-10 wt% and the content of the component (A2) is 99.9-90 wt% based on the total amount of the two components,

the component (A2) has an MFR (230 ℃ C., load of 2.16kg) of 1 to 500g/10 min,

ingredient (a2) is selected from the group consisting of:

(A2-1) propylene homopolymer,

And combinations thereof.

2. The resin composition according to claim 1, wherein the α -olefin in the component (a1) is ethylene.

3. The resin composition according to claim 2, wherein the intrinsic viscosity of the component (A1) is 23dl/g or more, and the content of ethylene is 3 to 30% by weight.

4. The resin composition according to claim 2 or 3, wherein,

Tm≥-3.4×C2+162...(1)。

5. a method for producing the resin composition according to any one of claims 1 to 4, comprising the steps of:

(b) An organoaluminum compound, and

the component (A1) is prepared by polymerizing the corresponding monomer according to the need (c) of a catalyst containing an external electron donor compound.

6. The resin composition according to any one of claims 1 to 4, which is obtained by a production method comprising a step of polymerizing monomers corresponding to the components (A1) and (A2) in 2 or more polymerization steps performed sequentially or continuously.

7. The resin composition according to claim 6, wherein the polymerization step of the monomer corresponding to the component (A1) comprises a prepolymerization step.

8. The resin composition according to any one of claims 1 to 4, 6 to 7, wherein MFR (230 ℃, load 2.16kg) is 1 to 20g/10 min.

9. The resin composition according to any one of claims 1 to 4 and 6 to 8, wherein the melt tension (200 ℃, diameter 2.095mm) is 2.5 to 30g by weight.

10. A foam formed from the resin composition described in any one of claims 1 to 4, 6 to 9.